Distillation process



June 26, 1945.. M. souDERS, JR

DISTILLATION PROCESS Filed July l, 1942 \-z parfs of A I5 Z paris of b Figi 50 60 70 8O 90 IOO Concen'l'rai'on of Solvems (Z bg Wt) IOO Fig. DI

Figli Patented June ze, 194s DISTILLATION PBOWSS Mott Souders, Jr., Piedmont, Calif., llsilnor to Shell Development Company, Ssn Francisco,

l Calif., a corporation of Delaware Application July 1, 1942, No. 449,348 l j z claims. l'cl. 2oz-4i) ',I'he present invention relates to a-method Fi'or' separating components of mixturesbyfdistillation. More particularly, it relates to distillation processes wherein components are separated by distillation in .the presence of a relatively high boiling selective solvent.

The process of extractive distillation .wherein' mixtures of components are separated by distillation in the presence of relatively high boiling solvents which alter the normal vapor pressure relart' isjan object of my invention to' provide en improvedextractive distillation process. Itisanl. other object to provide a method for-operating l extractive distillation'processes in the most eilitionships in a manner to aid separation has been successfully applied tothe separation of components which possess vapor pressures soisimilar that their separation is difilcult or even impossi- -ble in the absence 'of a relatively high boiling selective solvent or azeotrope-former.

Unfortunately, heretofore such separations have been poorly understood and as a result the application 'of such processes has dependedwholly upon empirical methods. Still further, this factor has hindered the wider application of this otherwise eminently suitable and widely applicable separation method.

It has been known for some time that the presence of a relatively high boiling selective solvent will markedly alter the vapor pressure of the component selectively dissolved as compared to that of the less soluble component. As a result this phenomenon may be employed to further accentuate or even reverse, the vapor pressure relationships existing between the components it is desired to separate. 'I'he less soluble com- Ponent is distilled overhead, while the more soluble component is withdrawn along withsolvent as `a bottom product. It has been further known that in general this Vapor pressure altering effect could be increased by increasing the solvent concentration. Keeping these principles in mind and adding the well known teaching of the distillation art, where it has long been recognized that for a given separation in a column equivalent to a given number of theoretical plates an increase in 'reux ratio increases the degree of separation attainable, it is not surprising that heretofore both large reflux ratios and high solvent-to-feed ratios have been applied in sometimes unsuccessful and frequently uneconomical attempts to apply extractive distillation to large scale commercial separation problems.

I have now discovered that these heretofore accepted principles applying to extractive distillation are not altogether true; for example, I have found that increased reux beyond a, certain critivcal value can beas harmful to a given separation as the failure to supply reflux up to a certainv critical value. I have discovered that to attain the most Iefficient and economical mode of opera- I tion it is necessary carefully to control and correlate the solvent and reflux rates in the manner hereinafter more fully described.

cient and economical manner., Further objects will be apparent from the following.

' 'The present invention comprises a, method for operating an extractive distillation system whereratio, and thesolvent concentration are so correlated as to result in over-all optimum eiilciency, as hereinafter more fully described.

It is desiredl to separate a feed mixture of X lparts of component A and 1-X parts of component B whichnormallyhave vapor pressures, or activities.: so similaras to make .their separation diillcult by Slmpledistillation in the absence of an azeotrope-former or selective-solvent' for 4 one of the components.

It is proposed'io lcarry out the separation by continuously distilling'thef mixture in the presence of. a relatively high boilingselective solvent Q for component B in a system represented by Fig. I which is a now diagram thereof. Referringto Fig. I, a feed mixture of components A andB (eachof which may be amixture or a pure compound) is fed via line i to column 2 equipped with reboller 3 and .operated at pressure P. SolventQ is to. be admitted to "co1umn 2 via .line 4 and ilowed down the extractive distillation zone of column. 2, i. e. the portion of column 2 below solvent. inlet i which contains a number of actual plates equivalenttoNtheoretical plates, VsolventQ exertingfits vapory pressure-altering effect on, component Band selectively dissolvingfit from ascending vapors ilowin'g countercurrentlythereto.

Vapors rich in component Aipassoverhead via line E to condenser i3.l Condensed vapors collect 'in accumulator 'i whence a portionoi the overhead is returned as reuxvia line B while the top product is withdrawn'via line` 9 and passed to storagel not shown. The portion of column 2 between.` reuxinlet 8, and v solventdnlet t is the stripping section and is. to be equivalentto a'.

sulcient number of theoretical plates so that with the reux-to-feed., ratio. l?. employed solvent Awill be prevented frompassing overhead with the top product. In some cases it is"desirable'to make this stripping section a'separate column.

At the outset'of'the problem, be it postulated that the feed mixture of X parts of A and I-X parts of B be separated into a topproduct of Y parts of A 'andl- Y. parts of B; while the bottom product is to be composed of .Z parts of A and 1-Z parts ofB. Therefore column 2 is to be operated so'that a bottom product consisting of Z- parts of A'and'1'-Z parts of B (on a solventfree basis) be withdrawn in solution of the solvent"from`thefbttom' of column 2 and pass via inthe reflux-to-feed ratio, the solvent-to-feed The problem is to iind the optimum solvent concentration (C) and the optimum` ratios of solvent-to-feed (S) and reilux-to-i'eed (R) which will produce the most emcient and economical separation set forth above, meeting the postulated conditions. To determine these optimum ratios proceed as follows:

First `step Determine experimentally the relative volatility oi.' A to B in the presence of various'concentrations of solvent Q.

the required `separation with the given extractive distillation zone of N plates is determined for each of the above alpha values.

This relationship may be determined by the method of Smoker (Transactions American Institute of Chemical Engineers, vol. 34, p. 165 (1938)), where the alpha values are independent oi' the relative proportions oi A to B; or according to the graphical Method of McCable and Thiele (Ind. Eng..Chem., vol. 17, p. 605 (1925)). For each of the above determined alpha values a corresponding minimum reflux ratiorfis thus obtained:

In most separations of substances closely related chemically, e. g. hydrocarbons differing only v in degree of saturation, the relative volatilities in the presence oi.' solvent do not vary appreciably with changes in the relative concentrations of -A and B in the mixture. For such separations it is only necessary to measure the relative volatilities of A to B for some convenient concentration (e. g. a 50-50. mixture of A'and B) for a series of different solvent concentrations C. In such cases it is convenient to measure the relative volatility of A to B in this 50-50 mixture and express this value as the alpha value, i. e. the equilibrium ratio of vapor concentration to liquid concentration for component A, divided by the similar ratio for component B.

In cases where the relative volatility o! components A and B varies appreciably with changes in their own relative concentration, itis usually necessary to determine the relative volatility for a series of mixtures containing diilerent relative concentrations of A and B and each series with vapor is in equilibrium. Special apparatus and.

techniques have been devisedfor conveniently determining relative volatilities (e. g. see Ind. Eng. Chem., Anal. ed., vol. 4, pp. 232-234 (1932) From the above measurements a series of relative volatility values (alpha values) are related to the various concentrations thus:

a1 corresponding to concentration Ci a: corresponding to concentration Cz as correspondng to concentration C:

a4 corresponding toconcentmtion C4 as corresponding to concentration Cs, etc.

Second step From'each of the above alpha values the corresponding minimum reflux ratio R is determined,

The minimum reflux ratios necessary to give Ri corresponding to a1 Rz corresponding to anv Ra corresponding to as R4 corresponding to a4 Rs corresponding to s y Thirdstep The solvent-feed rate necessary to maintain the solvent concentrations corresponding to the above calculated reflux ratios is determined.

This value is determined by substituting the above values in the formula Thus a series of values of S are determined corresponding to the various concentrations of solvent C thus:

Fourth step Determine the minimum solvent ratio from the o above data.

Plotting of the various values of S vs. C is a convenient way to determine this minimum as is illustrated by Fig. l1 which is a graph derived by such a plot. From Fig. Il.' it is seen that the minimum solvent-to-feed ratio is Sz.

According to the present invention the optimum solvent concentration, and solvent and re'- ilux ratios to apply in the above-separation are the values corresponding to the above minimum, that is, Ca, Ss and Rs, respectively. Accordingly, the extractive distillation process described' in the drawing is operated with solvent-to-feed ratios, solvent concentrations, and reux rates near values corresponding '-to the minimum available solvent-to-feed ratio.

Of course, it is not necessary to plot the above values; frequently the minimum value can be located by simple inspection of the data, preierably in tabular form.

EXAMPLE It is desired to separate a feed containing 48.5% beta-butylene and 51.5% butadiene by extract-ive distillation in a distillation system 'similarto the one described in Fig. I, employing an 83% acetone-17% water mixture as solvent. It is required that the'overhead product consist of 98% beta-butylene and that 98% of the beta-butylene in the feed be recovered as top product. The

bottom product comprising butadiene dissolved in solvent is to be withdrawn from the ilrst column and stripped from solvent in a second distillation column. It is decided to employ an extractive distillation column having an extractiva lows: The alpha values for mixtures of beta` butylene and butadiene are not appreciably in iluenced by changes in their relative proportions. Therefore, a series of mixtures corresponding to feed composition (48.5% beta-butylene and 51.5% butadiene) containing various proportions of solvent were made up and the relative volatilities determined.

The measurements were made at 120 lbs. per sq. in. pressure absolute and the alpha values were calculated for each of these mixtures. Re-

sults are tabulated in columns l and 2 of the table.

For each of these alpha values the minimuml reux required to obtain a given separation in a 60 plate column was determined by the method of Smoker. These values are tabulated in column 3 of the table.

By substitution in the formula.

wherein S=the solvent-tofeed ratio on weight basis, C=parts of solvent per part of solvent feed mixture (weight basis), and R=the minimum reflux-to-feed ratio for a 60 plate column, to attain the given separation, the solvent ratios corresponding to the above concentrations were calculated and are tabulated in column 4 of the table. From the values in the table the concentration of solvent was plotted as abscissas vs.' the corresponding solvent-to-feed ratios. plotted as ordinates, to give the graph of Fig. III. In accordance with these data the extractive distillation column is to be operated with a solvent-tofeed ratio of about 21.2 parts of solvent per part of feed by weight. andv at the corresponding reflux-to-feed ratio oi about 4.5 `parts of reflux per part of feed.

Table mum point of the curve because in general in extractive distillation processes the greatest expense is met in stripping and recircuiating the solvent. Thus. in the above example, the' opti- Y mum solvent-to-feed ratio lies between about 21.2 and 22.6 and the reiluxto-feed ratio lies between about 4.8 to 4.0. Moreover, contrary to the well-known teaching of the distillation art, it is not possible to improve the separation by increasing lthe reilux when operating with minimum solvent, since additional reilux reduces the solventy concentration and lowers the alpha value It will be understood that in any given case and locality, differences exist in the cost f heat, cooling water, pumping, etc., and-thus it is impossible to state exactly the most economical relation between reflux and solvent ratios where the l minima of the two do not coincide. However, in general, I have'found that the most economical conditions correspond to some value equal to or slightly greater than that value corresponding to the minimum solvent-to-feed ratio available (values below the minimum solvent-to-feed ratio will not permit the given separationto be attained). In accordance with these facts it will be realized that a certain amount of leeway must be given in choosing the i'lnal most economical conditions, and in some cases it may be desirable to choose to operate at some solvent-to-feed ratio and corresponding solvent concentration and reflux-to-feed ratio which is somewhat greater than the minimum, e.g. vup tovabout 1.5 times the minimum. However, other things being equal, if a value greater than the minimum is chosen it S such that the relationship between S and R is l l-C wherein C is the concentration of the solvent in Conc. Bbutylene in vapor Conc. -butylene in liquid Conc. butadiene in vapor Conc. butadiene in liquid atB. P. 12)# p. s. i. and equilibrium Weight per cent solvent (83% CHxCoCHi-l-U' Ha0)insolvent feed (43.5% p uzyxene-l-srg, butadiene) mixture Minimum reiiuxto-i'eed ratio 811in to mama... solvent conceneqlbm. plate ext. muon dstn. zone (wt. basis) the optimum conditions correspond to the miniY J5 the column such that the volatility ratio between the two components is substantially the minimum to permit their separation with said number of plates and said yreflux to feed ratio.

2. The method according to claim 1 wherein the solvent to feed ratio is less than 1.5 tim the minimum operative solvent to feed ratio as shown in Fig. Il.

MQTT. SOUDmS, Ja. 

